U.S. patent number 8,603,502 [Application Number 10/356,551] was granted by the patent office on 2013-12-10 for compositions comprising jasmonic acid derivatives and use of these derivatives.
This patent grant is currently assigned to L'Oreal S.A.. The grantee listed for this patent is Christophe Boulle, Maria Dalko, Jean-Luc Leveque, Lucie Simonetti. Invention is credited to Christophe Boulle, Maria Dalko, Jean-Luc Leveque, Lucie Simonetti.
United States Patent |
8,603,502 |
Boulle , et al. |
December 10, 2013 |
Compositions comprising jasmonic acid derivatives and use of these
derivatives
Abstract
Cosmetic or pharmaceutical compositions comprising compounds of
formula (I) and the corresponding salts thereof: ##STR00001##
wherein: R.sub.1 is a radical chosen from --COOR', --CONR'R'',
--CH.sub.2OR', --COR', --CH.sub.2R', --SO.sub.2OR', --PO.sub.3R'R''
and --NHR', wherein R' and R'', which may be identical or
different, are defined herein; R.sub.2 is chosen from saturated and
unsaturated, linear, branched and cyclic hydrocarbon radicals
comprising from 1 to 18 carbon atoms which are optionally
substituted by from 1 to 5 identical or different entities chosen
from --OR''', --OCOR''', --SR''', --SCOR''', NR'''R'''',
--NHCOR''', halogen, --CN, --COOR''' and --COR''', wherein R''' and
R'''', which may be identical or different, are defined herein, as
well as the use of these compounds, for example, to promote skin
desquamation, to stimulate epidermal renewal and/or to combat the
signs of skin ageing.
Inventors: |
Boulle; Christophe (Langy
S/Marne, FR), Dalko; Maria (Gif S/Yvette,
FR), Leveque; Jean-Luc (Paris, FR),
Simonetti; Lucie (Vincennes, FR) |
Applicant: |
Name |
City |
State |
Country |
Type |
Boulle; Christophe
Dalko; Maria
Leveque; Jean-Luc
Simonetti; Lucie |
Langy S/Marne
Gif S/Yvette
Paris
Vincennes |
N/A
N/A
N/A
N/A |
FR
FR
FR
FR |
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Assignee: |
L'Oreal S.A. (Paris,
FR)
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Family
ID: |
31499009 |
Appl.
No.: |
10/356,551 |
Filed: |
February 3, 2003 |
Prior Publication Data
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Document
Identifier |
Publication Date |
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US 20040029839 A1 |
Feb 12, 2004 |
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Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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60357620 |
Feb 20, 2002 |
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Foreign Application Priority Data
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Feb 4, 2002 [FR] |
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02 01279 |
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Current U.S.
Class: |
424/401; 514/573;
514/530 |
Current CPC
Class: |
C07C
35/06 (20130101); A61K 8/44 (20130101); C07C
59/11 (20130101); C07C 59/46 (20130101); C07C
69/732 (20130101); A61K 8/365 (20130101); C07C
69/675 (20130101); A61K 8/345 (20130101); A61Q
19/00 (20130101); A61Q 19/08 (20130101); A61Q
5/00 (20130101); A61Q 1/02 (20130101); C07C
2601/08 (20170501) |
Current International
Class: |
A61K
31/557 (20060101) |
Field of
Search: |
;514/530,573
;424/400,901 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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0 413 528 |
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Feb 1991 |
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EP |
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0 648 488 |
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Apr 1995 |
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EP |
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0 989 111 |
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Mar 2000 |
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EP |
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2718022 |
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Apr 1994 |
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FR |
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58-180410 |
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Oct 1983 |
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JP |
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A H3-188194 |
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Aug 1991 |
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JP |
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A H4-108761 |
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Apr 1992 |
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JP |
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A H7 308197 |
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Nov 1995 |
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JP |
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A H10-29935 |
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Feb 1998 |
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JP |
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T H11-511474 |
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Oct 1999 |
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JP |
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2001-199832 |
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Jul 2001 |
|
JP |
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2001-207188 |
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Jul 2001 |
|
JP |
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WO 93/10756 |
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Jun 1993 |
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WO |
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WO 96/00206 |
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Jan 1996 |
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WO |
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Other References
WO 96/00206 published Jan 4, 1996 (English abstract only). cited by
examiner .
Ansel's Pharmaceutical Dosage forms and Drug Delivery Systems,
2005, Lippincott Williams and Wilkins, (8.sup.th ed.), pp. 276-278.
cited by examiner .
Hiromasa Kiyota et al., "Lipase-catalyzed preparation of both
enantiomers of methyl jasomonate," Tetrahedron: Asymmetry, vol. 12,
No. 7, 2001, pp. 1035-1038. cited by applicant .
Database CA, Chemical Abstracts Service, Columbus, Ohio, US,
Database Accession No. 131:28910, XP002214852, 1999. cited by
applicant .
Database CA, Chemical Abstracts Service, Columbus, Ohio, US,
Database Accession No. 130-352121, XP002214853, 1999. cited by
applicant .
Database CA, Chemical Abstracts Service, Columbus, Ohio, US,
Database Accession No. 130:279324, XP002214854, 1999. cited by
applicant .
Database CA, Chemical Abstracts Service, Columbus, Ohio, US,
Database Accession No. 118:118844, XP002214855, 1999. cited by
applicant .
Co-pending Application No. Title: Compositions Comprising
Cyclopentant Derivatices and Their Use Inventor(s): Jean-Luc
Leveoue et al. U.S. Filing Date; Feb. 3, 2003. cited by applicant
.
English language abstract of JP 2001-207188, Jul. 31, 2000. cited
by applicant .
English language abstract of JP 58-180410, Oct. 21, 1983. cited by
applicant .
English language abstract of JP-A H7 308197, Nov. 28, 1995. cited
by applicant .
English language abstract of JP-A H10-29935, Mar. 3, 1998. cited by
applicant .
English language abstract of JP-A H3-188194 , Aug. 16, 1991. cited
by applicant .
English language abstract of JP-T-H11-511474, Oct. 5, 1999. cited
by applicant .
English language abstract of JP-A H4-108761, Apr. 9, 1992. cited by
applicant .
Herrmann, G., et al., "Biological Activity of Jasmonic Acid
Conjugates," Comjugated Plant Horm. Proc. Int. Symp., Meeting Date
1986, pp. 315-322 (1997). cited by applicant .
Ishikawa, A. et al., "Structure-Activity Relationships of
Jasmonates in the Induction of Expression of Two Proteinase
Inhibitor Genes of Potato," Bioscience, Biotechnology, and
Biochemistry, vol. 58(3), pp. 544-547, (1994). cited by applicant
.
Office Action mailed Dec. 27, 2005, in co-pending U.S. Appl. No.
10/356,628. cited by applicant .
Ward, K. et al., "The Induction of Proteinase Inhibitor II by
Jasmonates," Proceedings of the Plant Growth Regulator Society of
America, 23rd Edition, pp. 291-294, (1996). cited by
applicant.
|
Primary Examiner: Justice; Gina C
Attorney, Agent or Firm: Finnegan, Henderson, Farabow,
Garrett & Dunner, LLP
Parent Case Text
This application claims benefit of U.S. Provisional Application No.
60/357,620, filed Feb. 20, 2002.
Claims
What is claimed is:
1. A composition for skincare comprising a) a cosmetically or
pharmaceutically acceptable medium, b) at least one entity chosen
from compounds of formula (I) and the corresponding salts thereof:
##STR00013## wherein: R.sub.1 is a radical --COOH; R.sub.2 is
chosen from saturated linear, branched and cyclic hydrocarbon
radicals comprising from 1 to 8 carbon atoms and c) at least one
adjuvant chosen from a silicone oil, fluorinated oil, a gum, a wax,
a hydrophilic active agent, a lipophilic active agent, a
preservative, an antioxidant, a fragrance, a filler, a screening
agent, an odor absorber, and a colorant, wherein the composition is
effective for skincare.
2. The composition according to claim 1, wherein the radical
R.sub.2 is chosen from saturated linear hydrocarbon radicals
comprising from 2 to 6 carbon atoms.
3. The composition according to claim 2, wherein the radical
R.sub.2 is --(CH.sub.2).sub.4--CH.sub.3.
4. The composition according to claim 1, wherein the at least one
entity is chosen from: 3-hydroxy-2-pentylcyclopentaneacetic
acid.
5. The composition according to claim 1, wherein the at least one
entity is present in an amount ranging from 0.01 to 20% by weight,
relative to the total weight of the composition.
6. The composition according to claim 5, wherein the at least one
entity is present in an amount ranging from 0.5 to 10% by weight,
relative to the total weight of the composition.
7. The composition according to claim 6, wherein the at least one
entity is present in an amount ranging from 1 to 5% by weight,
relative to the total weight of the composition.
8. The composition according to claim 1, wherein the composition is
provided in a form chosen from; cleansing, protective, treatment
and care compositions for face, hands, feet, major anatomical folds
and body; facial and body makeup compositions; bath compositions;
deodorizing compositions; after-shave compositions; hair remover
compositions; and compositions to counter insect bites.
9. The composition according to claim 8, wherein the cleansing,
protective, treatment and care compositions for face, hands, feet,
major anatomical folds and body are chosen from day creams, night
creams, makeup remover creams, sunscreen compositions, protective
and care body milks, after-sun milks, skincare lotions, gels and
mousses, and artificial tanning compositions.
10. A pharmaceutical composition for skincare comprising a) a
pharmaceutically acceptable medium, b) at least one entity chosen
from compounds of formula (I) and the corresponding salts thereof:
##STR00014## wherein: R1 is a radical-COOH; R.sub.2 is chosen from
saturated, linear, branched and cyclic hydrocarbon radicals
comprising from 1 to 8 carbon atoms and c) at least one adjuvant
chosen from a silicone oil, fluorinated oil, a gum, a wax, a
hydrophilic active agent, a lipophilic active agent, a
preservative, an antioxidant, a fragrance, a filler, a screening
agent, an odor absorber, and a colorant, wherein the pharmaceutical
composition is effective for skincare.
11. The pharmaceutical composition according to claim 10, wherein
the pharmaceutical composition is effective to achieve at least one
effect chosen from promoting skin desquamation, stimulating
epidermal renewal, combating the signs of skin ageing, enhancing
facial complexion and smoothening the skin of a face.
12. The composition according to claim 1, wherein the at least one
entity is chosen from 3-hydroxy-2-pentylcyclopentane acetic acid of
the Formula: ##STR00015##
13. The composition according to claim 12, wherein the at least one
entity is present in an amount ranging from 0.01 to 20% by weight,
relative to the total weight of the composition.
14. The composition according to claim 13, wherein the at least one
entity is present in an amount ranging from 0.5 to 10% by weight,
relative to the total weight of the composition.
15. The composition according to claim 14, wherein the at least one
entity is present in an amount ranging from 1 to 5% by weight,
relative to the total weight of the composition.
16. A composition for skincare comprising, a) a cosmetically
acceptable medium, b) at least one entity, present in an amount
ranging from 0.01 to 20% by weight relative to the total weight of
the composition, chosen from compounds of formula (I) and the
corresponding salts thereof: ##STR00016## wherein: R.sub.1 is a
radical --COOR', wherein R' is chosen from a hydrogen atom and
saturated and unsaturated, linear, branched and cyclic hydrocarbon
radicals comprising from 1 to 18 carbon atoms; R.sub.2 is chosen
from saturated linear, branched and cyclic hydrocarbon radicals
comprising from 1 to 8 carbon atoms and c) at least one adjuvant
chosen from a silicone oil, fluorinated oil, a gum, a wax, a
hydrophilic active agent, a lipophilic active agent, a
preservative, an antioxidant, a fragrance, a filler, a screening
agent, an odor absorber, and a colorant, wherein the composition is
effective for skincare.
17. The composition according to claim 16, wherein the radical R1
is chosen from --COOR', wherein R' is chosen from a hydrogen atom
and saturated and unsaturated, linear, branched and cyclic
hydrocarbon radicals comprising from 1 to 12 carbon atoms.
18. The composition according to claim 17, wherein R' is chosen
from a hydrogen atom and saturated and unsaturated, linear,
branched and cyclic hydrocarbon radicals comprising from 1 to 8
carbon atoms.
19. The composition according to claim 16, wherein the radical R1
is chosen from the radicals --COOH, --COOCH.sub.3,
--COOC.sub.2H.sub.5, and --COOC.sub.3H.sub.7.
20. The composition according to claim 16, wherein R2 is chosen
from saturated and linear hydrocarbon radicals comprising from 2 to
6 carbon atoms.
21. The composition according to claim 20, wherein R.sub.2 is
--(CH.sub.2).sub.4--CH.sub.3.
22. The composition according to claim 16, wherein the at least one
entity is present in an amount ranging from 0.5 to 10% by weight,
relative to the total weight of the composition.
23. The composition according to claim 22, wherein the at least one
entity is present in an amount ranging from 1 to 5% by weight,
relative to the total weight of the composition.
24. The pharmaceutical composition according to claim 10, wherein
the at least one entity is 3-hydroxy-2-pentylcyclopentaneacetic
acid.
25. The composition according to claim 16, wherein the at least one
entity is chosen from 3-hydroxy-2-pentylcyclopentaneacetic
acid.
26. The cosmetic composition according to claim 16, wherein the
cosmetic composition is effective to achieve at least one effect
chosen from promoting skin desquamation, stimulating epidermal
renewal, combating the signs of skin ageing, enhancing facial
complexion, and smoothening the skin of a face.
27. The composition of claim 1, wherein the compound of formula (I)
is chosen from an alkali metal salt of the compound of formula
(I).
28. The composition of claim 4 wherein the compound of formula (I)
is chosen from an alkali metal salt of the compound of formula
(I).
29. The pharmaceutical composition for skincare of claim 10,
wherein the compound of formula (I) is chosen from an alkali metal
salt of the compound of formula (I).
30. The composition for skincare according to claim 12, wherein the
compound of formula (I) is chosen from an alkali metal salt of the
compound of formula (I).
31. The composition for skincare according to claim 16, wherein the
compound of formula (I) is chosen from an alkali metal salt of the
compound of formula (I).
32. The pharmaceutical composition for skincare according to claim
24, wherein the compound of formula (I) is chosen from an alkali
metal salt of the compound of formula (I).
33. The composition for skincare according to claim 25, wherein the
compound of formula (I) is chosen from an alkali metal salt of the
compound of formula (I).
Description
This disclosure relates to cosmetic or pharmaceutical compositions
comprising at least one jasmonic acid derivative. This disclosure
also relates to the use of a composition comprising at least one
jasmonic acid derivative, for example, to promote desquamation of
the skin, to stimulate epidermal renewal and/or to combat ageing of
the skin. This disclosure also relates to compositions, such as
cosmetic or pharmaceutical compositions, which may be employed to
promote desquamation of the skin and/or to stimulate epidermal
renewal and therefore to combat intrinsic and/or extrinsic
cutaneous ageing.
Desquamation is a natural phenomenon associated with the fact that
the epidermis, which constitutes the upper layer of the skin, is
continually being regenerated. The epidermis is composed of several
layers of cells, the deepest of which is the basal layer, which is
composed of undifferentiated cells. Over time, these cells
differentiate and migrate towards the surface of the epidermis,
making up the various layers thereof, until at the surface of the
epidermis they form the corneocytes, which are dead cells that may
be removed by desquamation. This loss at the surface is compensated
by the migration of cells from the basal layer towards the surface
of the epidermis. Thus, this phenomenon results in the perpetual
renewal of the skin. Forced removal of the horny layer can
accelerate the renewal and can make it possible to combat
ageing.
While the cells migrate towards the surface of the epidermis, they
continue their differentiation, until they reach the final stage,
known as the corneocyte. These are in fact dead cells which make up
the final layer of the epidermis, i.e., the outermost layer, also
known as the stratum corneum.
Cutaneous ageing resulting from intrinsic or extrinsic factors can
be manifested in the appearance of wrinkles and fine lines, in
yellowing of the skin (which develops a parchment-like aspect
accompanied by the appearance of pigmentary blemishes), in the
disorganization of the elastin and collagen fibres (leading to a
loss of elasticity, flexibility and firmness), or by the appearance
of telangiectases.
Some of these signs of ageing are more particularly associated with
intrinsic or physiological ageing, i.e. "normal" ageing, related to
age, or chronobiological ageing. Others are more specific to
extrinsic ageing, i.e. ageing brought about in general by the
environment; for example, photo-ageing due to exposure to the sun,
light, or any other radiation.
This disclosure concerns intrinsic or physiological ageing, as well
as extrinsic ageing.
The changes in the skin owing to intrinsic ageing may be the
consequence of a genetically programmed senescence involving
endogenous factors. This intrinsic ageing may result, for example,
in a slowdown in the renewal of the cells of the skin, which may be
reflected by the appearance of detrimental clinical changes or
histopathological changes. The clinical changes may include, for
example, a reduction in the subcutaneous adipose tissue and the
appearance of small wrinkles or fine lines. The histopathological
changes may include, for example, an increase in the number and
thickness of elastic fibres, a loss of vertical fibres from the
membrane of the elastic tissue, and the presence of large irregular
fibroblasts in the cells of this elastic tissue.
Extrinsic ageing may also lead to both detrimental clinical and
histopathological changes. The clinical changes may include, for
example, large wrinkles and the formation of a flaccid and
weathered skin. The histopathological changes may include, for
example, an excessive accumulation of elastic material in the upper
dermis and degeneration of the collagen fibres.
Various agents intended to combat cutaneous ageing are known in the
prior art.
U.S. Pat. No. 4,603,146 discloses the use of retinoic acid and its
derivatives in cosmetic compositions, for the purpose of combating
cutaneous ageing.
Moreover, many patents and publications (such as document EP-A-413
528) as well as many commercial cosmetic compositions teach the use
of .alpha.-hydroxy acids, such as lactic acid, glycolic acid or
citric acid, for treating cutaneous ageing.
In addition, .beta.-hydroxy acids, such as salicylic acid and its
derivatives, are known for their desquamating properties (see
document WO-A 93/10756 and U.S. Pat. No. 4,767,750).
All these compounds have an action against ageing of the skin by
promoting desquamation--i.e., the removal of the dead cells located
at the surface of the horny layer of the epidermis. This
desquamating property may also be referred to as a keratolytic
property.
However, the compounds of the prior art can also have side effects,
for example, stinging, stabbing pains, sensations of heat, and the
appearance of red blotches which can be unpleasant for the
user.
Thus, there is a need for anti-ageing agents that can minimize or
avoid at least one of the disadvantages of the prior art.
The inventors have surprisingly found that it is possible to
promote desquamation of the skin and/or stimulate epidermal
renewal, while possibly minimizing or avoiding at least one of the
disadvantages, for example, stinging, stabbing pains, sensations of
heat and red blotches which may be unpleasant for the user.
Accordingly, disclosed herein, is a cosmetic or pharmaceutical
composition comprising, in a physiologically acceptable medium, at
least one entity chosen from compounds of formula (I), as defined
below in paragraph [023], and the corresponding salts thereof. As
is evident from the structure of formula (I) set forth below in
paragraph [023], each compound of formula (I) contains at least
three assymetric carbons, which can also be referred to as chiral
centers, and thus each compound of formula (I) can represent at
least eight stereoisomers. As defined herein, the at least one
entity can be chosen from any combination of the stereoisomers of
formula (I), i.e., one stereoisomer, all stereoisomers, and more
than one stereoisomer but less than all stereoisomers.
Also disclosed herein is the use of the at least one entity to
prepare a pharmaceutical composition for caring for the skin, for
example, to promote desquamation of the skin, to stimulate
epidermal renewal, to combat the signs of skin ageing, to enhance
the complexion and/or to smoothen the skin of the face.
Further disclosed herein is the cosmetic use of the at least one
entity or a cosmetic composition comprising it, wherein the at
least one entity or cosmetic composition may be used for caring for
the skin, for example, to promote desquamation of the skin, to
stimulate epidermal renewal, to combat the signs of skin ageing, to
enhance the complexion and/or to smoothen the skin of the face.
Even further disclosed herein is a method of cosmetic treatment to
promote desquamation of the skin, to stimulate epidermal renewal,
to combat the signs of skin ageing, to enhance the complexion
and/or to smoothen the skin of the face, comprising applying to
skin a cosmetic composition as defined below.
It has been observed that the at least one entity disclosed herein
may present good solubility in water, which may facilitate the
utilization.
The at least one entity as disclosed herein and described above in
paragraph [018] is chosen from compounds of the following formula
(I) and the corresponding salts thereof:
##STR00002## wherein: R.sub.1 is a radical chosen from --COOR',
--CONR'R'', --CH.sub.2OR', --COR', --CH.sub.2R', --SO.sub.2OR',
--PO.sub.3R'R'' and --NHR', wherein R' and R'', which may be
identical or different, are chosen from a hydrogen atom and
saturated and unsaturated, linear, branched and cyclic hydrocarbon
radicals comprising from 1 to 18 carbon atoms, which may be
optionally substituted by from 1 to 5 identical or different
entities chosen from --OR''', --OCOR''', --SR''', --SCOR''',
NR'''R'''', --NHCOR''', halogen, --CN, --COOR''' and --COR''',
wherein R''' and R'''', which may be identical or different, are
chosen from a hydrogen atom, aryl radicals and saturated and
unsaturated, linear and branched hydrocarbon radicals comprising
from 1 to 4 carbon atoms; R.sub.2 is chosen from saturated and
unsaturated, linear, branched and cyclic hydrocarbon radicals,
comprising from 1 to 18 carbon atoms which may be optionally
substituted by from 1 to 5 identical or different entities chosen
from --OR''', --OCOR''', --SR''', --SCOR''', NR'''R'''',
--NHCOR''', halogen, --CN, --COOR''' and --COR''', wherein R''' and
R'''', which may be identical or different, are chosen from a
hydrogen atom, aryl radicals and saturated and unsaturated, linear
and branched hydrocarbon radicals comprising from 1 to 4 carbon
atoms.
In one embodiment, the radical R.sub.1 is chosen from --COOR',
--CONR'R'' and --CH.sub.2OR', wherein R' and R'', which may be
identical or different, are chosen from a hydrogen atom and
saturated and unsaturated, linear, branched and cyclic hydrocarbon
radicals comprising from 1 to 18 carbon atoms, for example, from 1
to 12 carbon atoms, and further, for example, from 1 to 8 carbon
atoms.
In another embodiment, the radical R.sub.1 is chosen from the
radicals --COOH, --CH.sub.2OH, --COOCH.sub.3, --COOC.sub.2H.sub.5,
--COOC.sub.3H.sub.7--CONHCH.sub.3 and --CONHC.sub.2H.sub.5.
In one embodiment, the radical R.sub.2 is chosen from saturated and
unsaturated, linear, branched, and cyclic hydrocarbon radicals
comprising from 1 to 18 carbon atoms, for example, from 1 to 12
carbon atoms, and further for example, from 1 to 8 carbon
atoms.
In another embodiment, the radical R.sub.2 is chosen from saturated
and linear hydrocarbon radicals comprising from 2 to 6 carbon atoms
and linear hydrocarbon radicals comprising a single double
unsaturation and comprising from 2 to 6 carbon atoms, and, for
example, a radical --CH.sub.2--CH.dbd.CH--C.sub.2H.sub.5 and,
further for example, a radical --(CH.sub.2).sub.4--CH.sub.3.
In one embodiment, the salts of the compounds of formula (I) which
may be used in accordance with this disclosure are chosen, for
example, from the alkali metal and alkaline earth metal salts, the
zinc, magnesium and strontium salts, salts with an organic amine,
and the quaternary ammonium salts.
In another embodiment, the salts of the compounds of formula (I)
according to this disclosure are chosen, for example, from the
salts of an acid chosen from organic and inorganic acids, such as
hydrochlorides, hydrobromides, and citrates.
In one embodiment, the at least one entity which may be used in the
context of this disclosure may be chosen from:
3-hydroxy-2-[(2Z)-2-pentenyl]cyclopentaneacetic acid, methyl
3-hydroxy-2-[(2Z)-2-pentenyl]cyclopentaneacetate,
2-[(2Z)-2-pentenyl]-3-hydroxycyclopentaneethanol,
3-hydroxy-2-pentylcyclopentaneacetic acid, methyl
3-hydroxy-2-pentylcyclopentaneacetate, and
2-pentyl-3-hydroxycyclopentaneethanol.
The amount of the at least one entity chosen from compounds of
formula (I) and the corresponding salts thereof, which may be used
in accordance with this disclosure, depends on the desired effect
and should be an amount effective for promoting desquamation of the
skin and/or stimulating epidermal renewal and therefore combating
intrinsic and/or extrinsic skin ageing.
In one embodiment, the amount of the at least one entity chosen
from compounds of formula (I) and the corresponding salts thereof,
which may be used in accordance with this disclosure, may range,
for example, from 0.01 to 20%, further, for example, from 0.5 to
10%, and even further, for example, from 1 to 5% by weight,
relative to the total weight of the composition.
The composition comprising the at least one entity chosen from
compounds of formula (I) and the corresponding salts thereof may
further comprise a physiologically acceptable medium, i.e., a
medium which is compatible with a keratin material such as skin,
scalp, nails, mucosae, eyes and hair or any other cutaneous region
of a body. This composition may be a cosmetic or pharmaceutical
composition and may therefore comprise a cosmetically or
pharmaceutically acceptable medium.
The physiologically acceptable medium may comprise water and at
least one organic solvent chosen, for example, from C.sub.1-C.sub.8
alcohols, for example, ethanol, isopropanol, tert-butanol and
n-butanol; polyols such as glycerol; glycols such as butylene
glycol, isoprene glycol, propylene glycol, and polyethylene glycols
such as PEG-8; and polyol ethers.
The composition may also comprise at least one fatty phase, which
may comprise at least one of oils, gums and waxes, which are
commonly used in the field of application in question. These oils,
gums, and waxes may be chosen, for example, from mineral oils
(liquid petrolatum), vegetable oils (liquid fraction of karite
butter, sunflower oil), animal oils (perhydrosqualene), synthetic
oils (purcellin oil), silicone oils and waxes (cyclomethicone) and
fluorinated oils (perfluoropolyethers), beeswax, carnauba wax and
paraffin wax. Fatty alcohols and fatty acids (stearic acid) may be
added to these oils.
When the composition is an emulsion, the proportion of the at least
one fatty phase may range, for example, from 5% to 80% by weight
and further, for example, from 5% to 50% by weight with respect to
the total weight of the composition. The oils, waxes, emulsifiers
and coemulsifiers used in the composition in the form of an
emulsion may be chosen from those conventionally used in the
cosmetics field. The emulsifier and the coemulsifier may be present
in the composition in a proportion ranging, for example, from 0.3%
to 30% by weight and further, for example, from 0.5 to 20% by
weight with respect to the total weight of the composition. In
addition, the emulsion may comprise at least one lipid vesicle.
When the composition is a solution or oily gel, the at least one
fatty phase may represent, for example, more than 90% by weight of
the total weight of the composition.
The composition may also comprise at least one adjuvant commonly
used in the field under consideration, chosen, for example, from
surfactants, emulsifiers, hydrophilic and lipophilic gelling
agents, hydrophilic and lipophilic additives, preservatives,
antioxidants, solvents, fragrances, fillers, screening agents,
odour absorbers and colourants. The amount of the at least one
adjuvant may be that conventionally used in the cosmetics field and
may range, for example, from 0.01% to 10% by weight of the total
weight of the composition. These adjuvants, depending on their
nature, may be introduced into the fatty phase, into the aqueous
phase and/or into the lipid spherules.
The surfactants, which can be used, include, for example, glycerol
stearate, polysorbate 60 and the PEG-6/PEG-32/Glycol Stearate
mixture sold under the name of Tefose.RTM. 63 by Gattefosse.
The hydrophilic gelling agents, which can be used, include, for
example, carboxyvinyl polymers (carbomer), acrylic copolymers, such
as acrylate/alkyl acrylate copolymers, polyacrylamides,
polysaccharides, such as hydroxypropylcellulose, natural gums and
clays. The lipophilic gelling agents include, for example, modified
clays, such as bentones, metal salts of fatty acids, such as
aluminium stearates, and hydrophobic silica, ethylcellulose and
polyethylene.
The hydrophilic active agents include, for example, proteins and
protein hydrolysates, amino acids, polyols, urea, allantoin, sugars
and sugar derivatives, water-soluble vitamins, plant extracts and
hydroxy acids.
The lipophilic active agents, including, for example, retinol
(vitamin A) and its derivatives, tocopherol (vitamin E) and its
derivatives, essential fatty acids, ceramides, essential oils, and
salicylic acid and its derivatives may be used.
As disclosed herein, the composition may comprise at least one
entity as defined above and at least one other active agent,
chosen, for example, from: agents which may improve hair re-growth
and/or act to slow down hair loss, for example, nicotinic esters,
for example, tocopherol nicotinate; benzyl nicotinate and
C.sub.1-C.sub.6 alkyl nicotinates, such as methyl and hexyl
nicotinates, pyrimidine derivatives, such as
2,4-diamino-6-piperidinopyrimidine 3-oxide or "Minoxidil"; and
agents which can promote hair re-growth, such as those disclosed by
European patent application No. 0 648 488; agents which can vary
cutaneous pigmentation and/or proliferation and/or differentiation,
such as retinoic acid and its isomers, retinol and its esters,
vitamin D and its derivatives, oestrogens, such as oestradiol,
kojic acid, and hydroquinone; antibacterials, such as clindamycin
phosphate, erythromycin and antibiotics from the tetracycline
class; agents for combating parasites, for example, metronidazole,
crotamiton and pyrethroids; antifungals, for example, compounds
belonging to the imidazole class, such as econazole, ketoconazole
and miconazole and their salts, polyene compounds, such as
amphotericin B, compounds of the allylamine family, such as
terbinafine, and alternatively octopirox; antiviral agents, such as
acyclovir; steroidal anti-inflammatory agents, such as
hydrocortisone, betamethasone valerate and clobetasol propionate,
and non-steroidal anti-inflammatory agents, such as, ibuprofen and
its salts, diclofenac and its salts, acetylsalicylic acid,
acetaminophen and glycyrrhizic acid; anaesthetic agents, such as
lidocaine hydrochloride and its derivatives; antipruritic agents,
such as thenaldine, trimeprazine and cyproheptadine; keratolytic
agents, such as .alpha.- and .beta.-hydroxycarboxylic acids and
.beta.-ketocarboxylic acids, their salts, amides and esters and,
for example, hydroxy acids, such as glycolic acid, lactic acid,
salicylic acid, citric acid and generally fruit acids, and
5-(n-octanoyl)salicylic acid; free-radical scavengers, such as
.alpha.-tocopherol and its esters, superoxide dismutases, certain
metal chelating agents and ascorbic acid and its esters;
antiseborrhoeics, such as progesterone; antidandruff agents, such
as octopirox and zinc pyrithione; antiacne agents, such as retinoic
acid and benzoyl peroxide; and extracts of plant, marine and
bacterial origin.
The composition may be provided in any envisageable pharmaceutical
form.
In one embodiment, the composition may be in a form chosen from
aqueous, alcoholic, aqueous-alcoholic and oily solutions;
dispersions of the lotion and serum type; water-in-oil,
oil-in-water and multiple emulsions; suspensions; microcapsules and
microparticles; vesicular dispersions of ionic and non-ionic type;
aqueous, oily and serum-form lotions; capsules, granules, syrups,
tablets; foams, solid preparations; and aerosol compositions
further comprising at least one pressurized propellant.
In another embodiment, the composition as disclosed herein may be
provided in a form of a haircare composition chosen from, for
example, a shampoo, a hairsetting lotion, a treatment lotion, a
styling cream and a styling gel, a dyeing composition, for example,
an oxidation dyeing composition, hair restructuring lotions, a
perming composition (for example, a composition for the first step
of a permanent waving treatment), a lotion and a gel for combating
hair loss and an antiparasitic shampoo.
In yet another embodiment, the composition may also be provided in
a form of a composition chosen from cleansing, protective,
treatment and care compositions for face, hands, feet, major
anatomical folds and body, for example, day creams, night creams,
makeup remover creams, sunscreen compositions, protective and care
body milks, after-sun milks, skincare lotions, gels and mousses,
such as cleansing lotions, artificial tanning compositions; facial
and body makeup compositions such as foundations; bath
compositions; deodorizing compositions comprising, for example, at
least one bactericide; after-shave compositions; hair remover
compositions; compositions to counter insect bites; pain relief
compositions; and compositions for treating certain diseases of the
skin, such as eczema, rosacea, psoriasis, lichens and severe
pruritus.
The composition as disclosed herein may be applied as a cosmetic or
pharmaceutical composition intended for the care of the skin of a
face, body or scalp, such as to promote skin desquamation,
stimulate epidermal renewal, combat the signs of skin ageing,
enhance the complexion and/or smoothen the skin of the face.
Embodiments described herein are illustrated in more detail in the
following non-limiting examples.
EXAMPLE 1
Synthesis of
(+/-)(1R,2R)-3-hydroxy-2-[(2Z)-2-pentenyl]cyclopentaneacetic acid
of formula
##STR00003##
Operation 1: Synthesis of (+/-)-jasmonic acid or
(+/-)(1R,2R)-3-oxo-2-[(2Z)-2-pentyl]cyclopentaneacetic acid
##STR00004##
In a 250 ml three-necked flask equipped with a condenser, a
thermometer and a magnetic stirrer, 15 g (66.9 mmol) of methyl
(+/-)-jasmonate were dissolved in 150 ml of acetone. 10 ml of
aqueous sodium hydroxide solution (5.35 g, 133.7 mmol) were added
slowly. The mixture was stirred at room temperature for 5 hours.
The acetone was then evaporated under vacuum and the residual
aqueous phase was subsequently washed with ethyl acetate
(2.times.30 ml). The aqueous phase was acidified to pH=2 using
hydrochloric acid and was then extracted with dichloromethane
(3.times.30 ml).
The organic phase was dried over sodium sulphate, filtered on
filter paper and then concentrated. The light brown oil obtained
was dried under vacuum.
This gave 13.6 g of (+/-)-jasmonic acid, i.e. a yield of 97%.
The .sup.1H NMR spectrum and the mass spectrum (negative
ionization) are in accordance with the expected structure.
Operation 2: Synthesis of
(+/-)(1R,2R)-3-hydroxy-2-[(2Z)-2-pentenyl]cyclopentaneacetic
acid
##STR00005##
In a 50 ml three-necked flask equipped with a condenser, a
thermometer and a magnetic stirrer, 1 g (4.8 mmol) of
(+/-)-jasmonic acid was dissolved in 15 ml of absolute ethanol. 430
mg (11.4 mmol) of sodium borohydride, NaBH.sub.4, were added. The
mixture was stirred at 50.degree. C. for 4 hours. When the reaction
was finished, 5 ml of water were added slowly. The precipitate
formed was filtered off. The filtrate was acidified to pH=5 with
hydrochloric acid and then extracted with ethyl acetate (3.times.30
ml). The organic phase was dried over sodium sulphate, filtered on
filter paper, and then concentrated. The colourless oil obtained
was purified by chromatography on silica gel (eluent:
dichloromethane/methanol). The colourless oil obtained was dried
under vacuum.
This gave 400 mg of the target compound, i.e. a yield of 40%.
The .sup.1H NMR spectrum is in accordance with the expected
structure.
EXAMPLE 2
Synthesis of
(+/-)(1R,2R)-2-[(2Z)-2-pentenyl]-3-hydroxycyclopentaneethanol of
Formula
##STR00006##
##STR00007##
In a 50 ml three-necked flask equipped with a condenser, a
thermometer and a magnetic stirrer, 1 g (4.5 mmol) of methyl
(+/-)-jasmonate was dissolved in 15 ml of tetrahydrofuran. 430 mg
(11.3 mmol) of lithium aluminium hydride, LiAlH.sub.4, were added.
The mixture was stirred at 50.degree. C. for 4 hours. When the
reaction was finished, 5 ml of water were added slowly. The
precipitate formed was filtered off and the filtrate was acidified
to pH=5 with hydrochloric acid and then extracted with ethyl
acetate (3.times.30 ml). The organic phase was dried over sodium
sulphate, filtered on filter paper, and then concentrated. The
colourless oil obtained was purified by chromatography on silica
gel (eluent: dichloromethane/methanol). The colourless oil obtained
was dried under vacuum.
This gave 550 mg of the target compound, i.e. a yield of 62%.
The .sup.1H NMR spectrum is in accordance with the expected
structure.
EXAMPLE 3
Synthesis of (+/-)(1R,2R)-3-hydroxy-2-pentylcyclopentaneacetic acid
of formula
##STR00008##
Operation 1: Synthesis of (+/-)-dihydrojasmonic acid or
(+/-)(1R,2R)-3-oxo-2-pentylcyclopentaneacetic acid of formula
##STR00009##
In a 250 ml three-necked flask equipped with a condenser, a
thermometer and a magnetic stirrer, 5 g (23.6 mmol) of methyl
(+/-)-dihydrojasmonate were dissolved in 50 ml of acetone. 10 ml of
aqueous sodium hydroxide solution (1.76 g, 44 mmol) were added
slowly. The mixture was stirred at room temperature for 5 hours.
The acetone was then distilled off under vacuum, and the residual
aqueous phase was then washed with ethyl acetate (2.times.20 ml).
The aqueous phase was acidified to pH=2 with hydrochloric acid.
This phase was then extracted with dichloromethane (2.times.30 ml).
The organic phase was dried over sodium sulphate, filtered on
filter paper, and then concentrated. The oil obtained was purified
by chromatography on silica gel (eluent: dichloromethane/methanol).
The oil obtained was dried under vacuum.
This gave 1.7 g of the target compound, i.e. a yield of 36%.
The .sup.1H NMR spectrum is in accordance with the expected
structure.
Operation 2: Synthesis of
(+/-)(1R,2R)-3-hydroxy-2-pentylcyclopentaneacetic acid
##STR00010##
This compound was prepared in a way similar to that described in
operation 2 of Example 1, by reacting dihydrojasmonic acid with
sodium borohydride, NaBH.sub.4, in ethanol at 50.degree. C. for 4
hours.
The target compound was obtained with a yield of 45%.
The .sup.1H NMR spectrum is in accordance with the expected
structure.
EXAMPLE 4
Synthesis of (+/-)(1R,2R)-2-pentyl-3-hydroxycyclopentaneethanol of
formula
##STR00011##
##STR00012##
This compound was prepared in a way similar to that described in
Example 2, by reacting methyl dihydrojasmonate in tetrahydrofuran
with lithium aluminium hydride at 50.degree. C. for 4 hours.
The target compound was obtained with a yield of 68%.
The .sup.1H NMR spectrum is in accordance with the expected
structure.
EXAMPLE 5
Activity Tests
The keratolytic power of a number of compounds of this disclosure
was studied. This test comprises counting corneocytes released
following incubation of patches of isolated stratum corneum in the
presence of the test compounds.
Stratum corneum isolated by trypsin/heat from surgical plasties was
used. A number of different stratum corneum samples were used.
Discs of 4 mm in diameter were punched out and placed at the bottom
of a 96-well plate.
Test 1
A 1% by weight solution of the compound of Example 3 was prepared
in a PBS buffer supplemented with 0.1% of Triton X100. The pH of
the solution was adjusted to 7.4.
50 microliters of test solution or of control solution (PBS buffer
supplemented with 0.1% of Triton X100) were added to each well.
Incubation was carried out at 37.degree. C. with stirring for 24
hours.
10 microliters of solution were then withdrawn and were placed in a
Malassez cell. The liberated corneocytes were counted under the
microscope.
The results obtained are as follows, expressed as the number of
liberated corneocytes per microliter, averaged over three tests.
Corneocyte fragments were not counted.
TABLE-US-00001 Sample 1* Sample 2* Sample 3* Average Example 3 28
.+-. 9 56 .+-. 7 101 .+-. 11 61 .+-. 33 Control 4 .+-. 4 8 .+-. 3
17 .+-. 8 9 .+-. 8 *average over three tests
The number of corneocytes liberated after incubation of the
isolated stratum corneum with the compound of this disclosure is
much greater than the number liberated in the presence of the
buffer on its own.
Test 2
A 1% by weight solution of the compound of Example 1, or jasmonic
acid (comparison), was prepared in a PBS buffer supplemented with
0.1% of Triton X100. The pH of the solution was adjusted to
7.4.
50 microliters of test solution or of control solution (PBS buffer
supplemented with 0.1% of Triton X100) were added to each well.
Incubation was carried out at 37.degree. C. with stirring for 24
hours.
10 microliters of solution were then withdrawn and were placed in a
Malassez cell. The liberated corneocytes were counted under the
microscope.
The results obtained are as follows, expressed as the number of
liberated corneocytes per microliter, averaged over three tests.
Corneocyte fragments are not counted.
TABLE-US-00002 Average (3 tests per sample, 3 different samples)
Example 1 26 .+-. 7 Jasmonic acid 15 .+-. 5 Control 9 .+-. 3
Test 3
A 2% by weight solution of the compound of Example 3, or
2-hydroxy-4-octanoylbenzoic acid (comparison), was prepared in an
aqueous solution containing 50% by weight of polyethylene glycol
(PEG 8) and 30% by weight of ethanol.
50 microliters of test solution or of control solution were added
to each well. Incubation was carried out at 37.degree. C. with
stirring for 24 hours.
10 microliters of solution were then withdrawn and were placed in a
Mallassez cell. The liberated corneocytes were counted under the
microscope.
The results obtained are as follows, expressed as the number of
liberated corneocytes per microliter, averaged over the three
tests. Corneocyte fragments were not counted.
TABLE-US-00003 Sample 1* Sample 2* Average Example 3 2 .+-. 3 3
.+-. 1 2.5 .+-. 2 2-Hydroxy-4- 3 .+-. 3 4 .+-. 3 3.5 .+-. 3
octanoylbenzoic acid Control 1 .+-. 1 1 .+-. 1 1 .+-. 1 *Average
over three tests
EXAMPLE 6
An emulsion was prepared comprising (% by weight):
TABLE-US-00004 compound of Example 1 1% propylene glycol
isostearate 13% polyethylene glycol (8 EO) 5% propylene glycol 3%
pentylene glycol 3% glyceryl stearate and polyethylene glycol 5%
stearate (100 EO) ethoxylated sorbitan monostearate (20 EO) 0.5%
ethoxylated (20 EO) and propoxylated (5 PO) 1% cetyl alcohol
gelling agent 0.5% C.sub.12 15 alkyl benzoates 4% ethanol 3% sodium
hydroxide 0.12% preservatives qs water qs 100%
* * * * *